1. Field of the Invention
This invention relates to a catalytic method for the preparation of diazabicyclo-(2.2.2.)-octane (triethylenediamine). More particularly, this invention relates to a catalytic method for the manufacture of triethylenediamine from hydroxyethyl derivatives of cyclic and acyclic. Still more particularly, this invention is directed to the use of titania and zirconia catalysts to which a minor amount of phosphorus has been thermally chemically bonded at the surface thereof in the form of phosphate linkages. Even more particularly, the present invention is directed a continuous process for the manufacture of triethylenediamine from hydroxyethyl derivatives of cyclic and acyclic ethylenepolyamines by passing such feedstocks over a bed of catalyst in a reaction zone wherein the catalyst is composed of pellets of titania and/or zirconia to which a minor amount of phosphorus (0.5 to 7 wt. %) has been thermally chemically bonded to the surface in the form of phosphate linkages.
2. Prior Art
The catalysts used in the practice of the process of the present invention are disclosed in Vanderpool U.S. Pat. No. 4,588,842, a division of abandoned Vanderpool U.S. application Ser. No. 455,160, filed Jan. 3, 1983, upon which is based European patent application Ser. No. 83,307,520.3 published Aug. 28, 1984, wherein they are disclosed as useful in promoting the reaction of ethylenediamine with ethanolamine to provide essentially linear polyethylenepolyamine reaction products. Minor quantities of cyclic products are also formed.
It has heretofore been proposed to manufacture triethylenediamine from a wide variety of cyclic and acyclic polyethylenepolyamines. For example, it has been proposed to use solid cracking catalysts such as silica-alumina cracking catalysts to manufacture triethylenediamine from feedstocks such as polyethylenepolyamines (Herrick U.S. Pat. No. 2,937,176), from mixtures of diethanolamine with ethylenediamine (Mascioll U.S. Pat. No. 2,977,364), from N-aminoethyl piperazine (Krause U.S. Pat. No. 2,985,658), and from mixed feedstocks such as a feedstock containing both cyclic and acyclic polyethylenepolyamines such as N-aminoethyl piperazine and hydroxyethyl piperazine, diethylenetriamine and aminoethylethanolamine (Brader et al. U.S. Pat. No. 3,231,573). Brader U.S. Pat. No. 3,157,657 discloses the preparation of triethylenediamine from N-aminoethyl piperazine using a catalyst comprising tungsten or a base modified silica alumina cracking catalyst (Brader U.S. Pat. No. 3,120,526). U.S. Pat. No. 3,080,371 discloses the use of an organic carboxylic acid to catalyze the conversion of hydroxyethyl piperazine to triethylenediamine.
Brader et al. U.S. Pat. No. 3,297,701 discloses a method for the preparation of triethylenediamine by bringing an appropriate feedstock such as a cyclic or acyclic polyethylenepolyamine (e.g., N-aminoethyl piperazine, monoethanolamine, etc.) into contact with a phosphate of an enumerated metal (e.g., aluminum, calcium or iron phosphate). Also, Brader et al. propose the use of 2-(2-hydroxyethoxy)ethylamine as a feedstock for the synthesis of triethylenediamine in U.S. Pat. No. 3,172,891 using an aluminum phosphate catalyst.
Muhlbauer et al. U.S. Pat. No. 3,285,920 is directed to a continuous process for the manufacture of piperazine and triethylenediamine wherein N-aminoethyl piperazine is converted to triethylenediamine using a silica-alumina cracking catalyst alone or modified with alkaline earth metal oxides, alkali metal oxides, zirconia, etc., a tungsten catalyst or a phosphate salt such as a phosphate salt of aluminum or iron.
In Wells U.S. Pat. No. 4,405,784, a method for the manufacture of triethylenediamine from a cyclic or acyclic polyethylenepolyamine is discloses wherein the catalyst that is used is strontium diorthophosphate.